Jessica Avivar

Fully automated lab-on-valve-multisyringe flow injection analysis-ICP-MS system: an effective tool for fast, sensitive and selective determination of thorium and uranium at environmental levels exploiting solid phase extraction

An on-line solid-phase extraction method linked to inductively coupled mass spectrometry (ICP-MS) has been developed for the determination of low levels of uranium and thorium in environmental samples. The hyphenation of lab-on-valve (LOV) and multisyringe flow injection analysis (MSFIA), coupled to an ICP-MS, allows the simultaneous determination of thorium and uranium in different types of environmental sample matrices achieving high selectivity and sensitivity levels. On-line separation and preconcentration of thorium and uranium are carried out by means of UTEVA resin. The potential of the LOV-MSFIA makes possible the full automation of the system by the on-line regeneration of the column. The limits of detection reached are 0.4 ng L−1 of uranium and 2.8 ng L−1 of thorium. The reproducibility of the LOV-MSFIA-ICP-MS is 1.7% of RSD. Moreover, a high sensitivity, a wide working range (0–200 μg L−1 for uranium and thorium) and an injection frequency up to 9 h−1 (depending on the sample volume) should be highlighted. Different water sample matrices (seawater, well water, freshwater, tap water and mineral water), a phosphogypsum sample with natural uranium and thorium content and a channel sediment reference material were satisfactorily analyzed with the proposed method.

Lab on valve-multisyringe flow injection system (LOV-MSFIA) for fully automated uranium determination in environmental samples.

The hyphenation of lab-on-valve (LOV) and multisyringe flow analysis (MSFIA), coupled to a long path length liquid waveguide capillary cell (LWCC), allows the spectrophotometric determination of uranium in different types of environmental sample matrices, without any manual pre-treatment, and achieving high selectivity and sensitivity levels. On-line separation and preconcentration of uranium is carried out by means of UTEVA resin. The potential of the LOV-MSFIA makes possible the fully automation of the system by the in-line regeneration of the column. After elution, uranium(VI) is spectrophotometrically detected after reaction with arsenazo-III. The determination of levels of uranium present in environmental samples is required in order to establish an environmental control. Thus, we propose a rapid, cheap and fully automated method to determine uranium(VI) in environmental samples. The limit of detection reached is 1.9 ηg of uranium and depending on the preconcentrated volume; it results in ppt levels (10.3 ηg L(-1)). Different water sample matrices (seawater, well water, freshwater, tap water and mineral water) and a phosphogypsum sample (with natural uranium content) were satisfactorily analyzed.

Estrogens determination in wastewater samples by automatic in-syringe dispersive liquid-liquid microextraction prior silylation and gas chromatography.

A new procedure for the extraction, preconcentration and simultaneous determination of the estrogens most used in contraception pharmaceuticals (estrone, 17β-estradiol, estriol, and 17α-ethynylestradiol), cataloged as Contaminants of Emergent Concern by the Environmental Protection Agency of the United States (US-EPA), is proposed. The developed system performs an in-syringe magnetic stirring-assisted dispersive liquid-liquid microextraction (in-syringe-MSA-DLLME) prior derivatization and gas chromatography (GC-MS). Different extraction (carbon tetrachloride, ethyl acetate, chloroform and trichloroethylene) and disperser solvents (acetone, acetonitrile and methanol) were tested. Chloroform and acetone were chosen as extraction and disperser solvent, respectively, as they provided the best extraction efficiency. Then, a multivariate optimization of the extraction conditions was carried out. Derivatization conditions were also studied to ensure the conversion of the estrogens to their respective trimethylsilyl derivatives. Low LODs and LOQs were achieved, i.e. between 11 and 82ngL(-1), and 37 and 272ngL(-1), respectively. Good values for intra and inter-day precision were obtained (RSDs≤7.06% and RSD≤7.11%, respectively). The method was successfully applied to wastewater samples.

Automated total and radioactive strontium separation and preconcentration in samples of environmental interest exploiting a lab-on-valve system

A novel lab-on-valve system has been developed for strontium determination in environmental samples. Miniaturized lab-on-valve system potentially offers facilities to allow any kind of chemical and physical processes, including fluidic and microcarrier bead control, homogenous reaction and liquid-solid interaction. A rapid, inexpensive and fully automated method for the separation and preconcentration of total and radioactive strontium, using a solid phase extraction material (Sr-Resin), has been developed. Total strontium concentrations are determined by ICP-OES and (90)Sr activities by a low background proportional counter. The method has been successfully applied to different water samples of environmental interest. The proposed system offers minimization of sample handling, drastic reduction of reagent volume, improvement of the reproducibility and sample throughput and attains a significant decrease of both time and cost per analysis. The LLD of the total Sr reached is 1.8ng and the minimum detectable activity for (90)Sr is 0.008Bq. The repeatability of the separation procedure is 1.2% (n=10).

In-syringe magnetic stirring-assisted dispersive liquid-liquid microextraction and silylation prior gas chromatography-mass spectrometry for ultraviolet filters determination in environmental water samples.

A novel online approach involving in-syringe magnetic stirring assisted dispersive liquid-liquid microextraction and derivatization coupled to gas chromatography-mass spectrometry has been developed for the determination of seven UV filters extensively used in cosmetic products in environmental water samples. The effect of parameters such as the type and volume of extraction solvent, dispersive solvent and derivatization agent, pH, ionic strength and stirring time, was studied using multivariate experimental design. Extraction, derivatization and preconcentration were simultaneously performed using acetone as dispersive solvent, N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) as derivatization agent and trichloroethylene as extraction solvent. After stirring during 160s, the sedimented phase was transferred to a rotary micro-volume injection valve (3 μL) and introduced by an air stream into the injector of the GC through a stainless-steel tube used as interface. The detection limits were in the range of 0.023-0.16 μg L(-1) and good linearity was observed up to 500 μg L(-1) of the studied UV filters, with R(2) ranging between 0.9829 and 0.9963. The inter-day precision expressed as relative standard deviation (n=5) varied between 5.5 and 16.8%. Finally, the developed method was satisfactorily applied to assess the occurrence of the studied UV filters in seawater and pool water samples. Some of the studied UV filters were found in these samples and an add-recovery test was also successfully performed with recoveries between 82 and 111%.

Parabens determination in cosmetic and personal care products exploiting a multi-syringe chromatographic (MSC) system and chemiluminescent detection

Parabens are widely used in dairy products, such as in cosmetics and personal care products. Thus, in this work a multi-syringe chromatographic (MSC) system is proposed for the first time for the determination of four parabens: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP) in cosmetics and personal care products, as a simpler, practical, and low cost alternative to HPLC methods. Separation was achieved using a 5mm-long precolumn of reversed phase C18 and multi-isocratic separation, i.e. using two consecutive mobile phases, 12:88 acetonitrile:water and 28:72 acetonitrile:water. The use of a multi-syringe buret allowed the easy implementation of chemiluminescent (CL) detection after separation. The chemiluminescent detection is based on the reduction of Ce(IV) by p-hydroxybenzoic acid, product of the acid hydrolysis of parabens, to excite rhodamine 6G (Rho 6G) and measure the resulting light emission. Multivariate designs combined with the concepts of multiple response treatments and desirability functions have been employed to simultaneously optimize and evaluate the responses. The optimized method has proved to be sensitive and precise, obtaining limits of detection between 20 and 40 µg L(-1) and RSD <4.9% in all cases. The method was satisfactorily applied to cosmetics and personal care products, obtaining no significant differences at a confidence level of 95% comparing with the HPLC reference method.

Automation of 99Tc extraction by LOV prior ICP-MS detection: Application to environmental samples

A new, fast, automated and inexpensive sample pre-treatment method for (99)Tc determination by inductively coupled plasma-mass spectrometry (ICP-MS) detection is presented. The miniaturized approach is based on a lab-on-valve (LOV) system, allowing automatic separation and preconcentration of (99)Tc. Selectivity is provided by the solid phase extraction system used (TEVA resin) which retains selectively pertechnetate ion in diluted nitric acid solution. The proposed system has some advantages such as minimization of sample handling, reduction of reagents volume, improvement of intermediate precision and sample throughput, offering a significant decrease of both time and cost per analysis in comparison to other flow techniques and batch methods. The proposed LOV system has been successfully applied to different samples of environmental interest (water and soil) with satisfactory recoveries, between 94% and 98%. The detection limit (LOD) of the developed method is 0.005 ng. The high durability of the resin and its low amount (32 mg), its good intermediate precision (RSD 3.8%) and repeatability (RSD 2%) and its high extraction frequency (up to 5 h(-1)) makes this method an inexpensive, high precision and fast tool for monitoring (99)Tc in environmental samples.

Automatic and Simple Method for 99Tc Determination Using a Selective Resin and Liquid Scintillation Detection Applied to Urine Samples

(99m)Tc (6.0067 h half-life) is an artificial radionuclide largely used in diagnostic medicine. Its daughter (99)Tc is a beta emitter of great concern because of its long half-life (2.111 × 10(5) years) and presumed mobile behavior in the environment. To monitor the (99)Tc in urine from treated patients, an automatic Lab-on-valve (LOV) system for separation and preconcentration of (99)Tc was developed. TEVA resin was selected since it retains pertechnetate ion selectively from diluted nitric acid solutions. After elution, (99)Tc is detected using a liquid scintillation counting (LSC) detector. The present method has been successfully applied to urine samples with low (99)Tc content (recoveries between 94-111%). The minimum detectable activity (MDA) of the developed method is 0.1 Bq or 1 Bq L(-1) (expressed as activity concentration), when preconcentrating 100 mL of sample. The high durability of the resin, together with the low amount of resin required (32 mg), the good reproducibility (RSD 2%, n = 5) and the high extraction frequency (up to 12 h(-1)) makes of the present method an inexpensive, precise and fast useful tool for monitoring (99)Tc in urine samples.

Laboratory automation based on flow techniques

Flow techniques have undoubtedly aroused special interest in relation to many other automatic methodologies of analysis. Ever since segmented flow analysis (SFA) was developed by Skeggs in 1957, flow techniques have been in continuous evolution toward new develop-ments. There is no solid argument in favor of using any particular flow technique separately; rather, substantial advantages can be derived from their combination. Since flow-based methods are nonseparative tools, the advantages of combining flow techniques with separation techniques are noteworthy. High selectivity can be achieved by coupling them with liquid chromatography (LC), gas chromatography (GC), solid-phase extraction (SPE), or capillary electrophoresis (CE). Thus, a detailed description of flow techniques, their evolution, their hyphenation advantages, and a critical comparison between current developed methods exploiting flow techniques aimed at solving present analytical needs are reviewed in this article.

Uranium monitoring tool for rapid analysis of environmental samples based on automated liquid-liquid microextraction

A fully automated in-syringe (IS) magnetic stirring assisted (MSA) liquid-liquid microextraction (LLME) method for uranium(VI) determination was developed, exploiting a long path-length liquid waveguide capillary cell (LWCC) with spectrophotometric detection. On-line extraction of uranium was performed within a glass syringe containing a magnetic stirrer for homogenization of the sample and the successive reagents: cyanex-272 in dodecane as extractant, EDTA as interference eliminator, hydrochloric acid to make the back-extraction of U(VI) and arsenazo-III as chromogenic reagent to accomplish the spectrophotometric detection at 655 nm. Magnetic stirring assistance was performed by a specially designed driving device placed around the syringe body creating a rotating magnetic field in the syringe, and forcing the rotation of the stirring bar located inside the syringe. The detection limit (LOD) of the developed method is 3.2 µg L(-1). Its good interday precision (Relative Standard Deviation, RSD 3.3%), and its high extraction frequency (up to 6 h(-1)) makes of this method an inexpensive and fast screening tool for monitoring uranium(VI) in environmental samples. It was successfully applied to different environmental matrices: channel sediment certified reference material (BCR-320R), soil and phosphogypsum reference materials, and natural water samples, with recoveries close to 100%.